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Benzoboradioxacyclohexadienes and Benzoazaboraoxacyclohexadienes.

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Consequently, by analogy to compounds containing water
of crystallization, it seems as though a distinction must be
made with ammoniates between “structural ammonia” and
“coordinated ammonia”. Since the coordinatively bonded
ammonia ought not to react with carbon dioxide, the reaction
of ammoniates with carbon dioxide should provide a means
for differentiating between structural and coordinated ammonia.
Received: February 26th, 1965 [Z 937/763 IE]
German version: Angew. Chem. 77, 453 (1965)
[ I ] W. Peters, Ber. dtsch. chem. Ges. 42, 4826 (1909);Z.anorg.
Chem. 77, 159 (1912).
[2] G. Beck, Z . anorg. allg. Chem. 206, 416 (1932).
[ 3 ] P. Spacu, Z. anorg. allg. Chem. 230, 181 (1936).
[4] J. Knlnine and G. Gibson, J. inorg. nucl. Chem. 7, 5 5 (1958).
briefly. The products crystallize out on cooling, generally in
yields of about 70%, and can be recrystallized from ethanol/
benzene (about I :I). They melt without decomposition and
are stable i n air, in the solid state and in solution, even in neutral or weakly acidic aqueous solutions. They arc decomposcd
by aqueous alkalies.
If the azomethines of salicylaldehyde obtained with aniline or
o-aminophenol are treated with Flavognost& (P-aminoethyl
diphenylborinate) instead of with tetraphenyldiboron oxide,
then (2e) is formed instead of (211 or ( 2 g ) .
Received: March Ist, 1965
[Z 9261752 IE]
German version. Angew. Chem. 7 7 , 426 (1965)
Ill
D. Kustner, Angew. Chem. 54, 273, 296 (1941).
Synthesis of N-Phenyl-S-chloroisothiocarbamoyl
Chlorides by Chlorination of Isothiocyanates [*]
Benzoboradioxacyclohexadienes and
Benzoazaboraoxacyclohexadienes
By Dr. G. Ottmann and H . Hooks, Jr.
By Prof. Dr. F. Umland and Dip1.-Chem. C. Schleyerbach
Anorganisch-Chemisches Institut der Universitat Miinster
and
Institut fur Anorganische Chemie der Technischen
Hochschule Hannover (Germany)
The reaction of equimolar amounts of salicylaldehyde and
diphenylborinic acid or its anhydride (tetraphenyldiboron
oxide) leads to 3,3-diphenyl-3-bora-2,4-dioxabenzocyclohexa1,5-diene ( I ) , which has the same basic skeleton as a complex
prepared from acetophenone and boron trifluoride by
Kiistner [I].
Olin Mathieson Chemical Corporation, Chemicals Division,
New Haven, Conn. (U. S. A,)
During the preparation of phenyl isocyanide dichloride from
the corresponding isothiocyanate and chlorine, Helmers [ I ]
isolated an unstable adduct, to which Dyson and Hurrington[Z]
assigned the structure ( I ) .
H
H
We have now found that the first step of the chlorination of
phenyl isothiocyanates consists of the addition of one mole of
chlorine onto one isothiocyanato group to form N-phenyl-Schloroisothiocarbamoyl chlorides (2), a hitherto unknown
class of compounds. The compound ( I ) is merely a by-product formed in a side reaction.
21
(1 )
When the reaction is conducted in the presence of amines or,
preferably, when azomethine derivatives of salicylaldehyde
are condensed with diphenylborinic acid, derivatives of the
hitherto unknown ring system 3,3-diphenyl-2-aza-3-bora-4oxabenzocyclohexa- 1,5-diene (2) are formed.
R
M . p.
10-3
Color 01 solid
[ OCI
151
193
157
103
I04
145
154
159
M 236
M 325
S 370
M 280
M 375
M 259
M 305
M 239
M 360
S 402
M 239
M 360
S 402
M 280
M 370
M 269
M 337
M 355
M 418
13.0
2.7
1.0
8.0
2.5
10.0
3.0
11.0
2.0
I .o
12.0
2.5
1.o
10.0
3.5
10.0
8.0
9.5
9.5
bright yellow
pale yellow
white
pale yellow
Ph-NCS
CI
A
/scl
Ph-iG;=C\
Cl
Cl
I _ Ph-NCC12
+ SClz
(2j
N-Phenyl-S-chloroisothiocarbamoylchlorides (2) can be
prepared in a pure state and in high yields by treating aromatic isothiocyanates in an indifferent solvent at 0- 10 OC
with one mole of chlorine per -NCS group. The solid
representatives can be purified by recrystallization from
pentane or hexane.
We have prepared the following derivatives: N-phenyl-Schloroisothiocarbamoyl chloride (3) [yellow oil, n’,” =
1.6291 ; 91.5% yield], N,N’-phenylene-l,4-bis-(S-chloroisothiocarbamoyl chloride) ( 4 ) [yellow crystals, m.p. 82-83 OC;
97. 8 73,and N,N’-toluylene-2,4-bis-(S-chloroisothiocarbamoyl chloride) ( 5 ) [yellow crystals, m.p. 75-75.5 ‘C; 65 %I.
yellow
pale yellow
ochre yellow
lemon yellow
[a] In methanol; M = maximum, S = shoulder.
Equimolar amounts of the azomethines and tetraphenyldiboron oxide were dissolved separately in ethanol or ethanol/
benzene (1 : 1 v/v), and the solutions were mixed and boiled
432
Their structures are supported by combustion analysis, molecular weight determination, infrared and N M R spectroscopy,
and by their chemicaI reactions which will be the subject of
forthcoming publications. The N-phenyl-S-chloroisothioAngew. Chem. internat. Edit. / Vol. 4 (1965)
/ No. 5
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